Fungicides

ABSTRACT

Compounds having the formula (I): ##STR1## in which any two of K, L and M are nitrogen and the other is CE; X and Y are independently hydrogen, halogen, C 1-4  alkyl, C 3-6  cycloalkyl, C 2-4  alkenyl, C 2-4  alkynyl, C 2-4  alkynyloxy, phenyl, benzyloxy, cyano, isocyano, isothiocyanato, nitro, NR 1  R 2 , NR 1  OR 2 ,N 3 , NHCOR 1 , NR 1  CO 2  R 2 , NHCONR 1  R 2 , N═CHNR 1  R 2 , NHSO 2  R 1 , OR 1 , OCOR 1 , OSO 2  R 1 , SR 1 , SOR 1 , SO 2  R 1 , SO 2  OR 1 , SO 2  NR 1  R 2 , COR 1 , CR 1  ═NOR 2 , CHR 1  CO 2  R 2 , CO 2  R 1 , CONR 1  R 2 , CSNR 1  R 2 , CH 3  O 2  C.C:CH.OCH 3 , 1-(imidazol-1-yl)vinyl, a 5-membered heterocyclic ring containing one, two or three nitrogen heteroatoms, or a 5- or 6-membered heterocyclic ring containing one or two oxygen or sulphur hetero-atoms, optionally a nitrogen heteroatom and optionally one or two oxo or thioxo substituents; or X and Y, when ortho to one another, join to form a 5- or 6-membered aliphatic or aromatic ring optionally containing one or two oxygen, sulphur or nitrogen atoms or one, two or three nitrogen atoms; A, B, D, E, G, U and V are independently hydrogen, halogen, C 1-4  alkyl C 1-4  alkoxy, cyano, nitro or trifluoromethyl; and R 1  and R 2  are independently hydrogen, C 1-4  alkyl, C 2-4  alkenyl or phenyl; the aliphatic moieties of any of the foregoing being optionally substituted with one or more of halogen, cyano, OR 1 , SR 1 , NR 1  R 2 , SiR 1   3  or OCOR 1  and the phenyl moieties of any of the foregoing being optionally substituted with one or more of halogen, C 1-4  alkyl, C 1-4  alkoxy, nitro or cyano. The compounds are useful as fungicides.

This is a division of application Ser. No. 07/818,431, filed Dec. 27,1991, now U.S. Pat. No. 5,145,856, which is a continuation of Ser. No.07/478,403, filed Feb. 12, 1990, now abandoned.

This invention relates to derivatives of propenoic acid useful asfungicides, to processes for preparing them, to fungicidal compositionscontaining them, and to methods of using them to combat fungi,especially fungal infections of plants.

A range of pesticidal alkyl 2-(substituted)pyridinyl- andpyrimidinyloxyphenyl-3-alkoxypropenoates is described in EP-A-0242081.

According to the present invention there are provided pyrimidines havingthe formula (I): ##STR2## in which any two of K, L and M are nitrogenand the other is CE; X and Y are independently hydrogen, halogen, C₁₋₄alkyl, C₃₋₆ cycloalkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₂₋₄ alkynyloxy,phenyl, benzyloxy, cyano, isocyano thiocyanato, isothiocyanato, nitro,NR¹ R², NR¹ OR², N₃, NHCOR¹, NR¹ CO₂ R², NHCONR¹ R², N═CHNR¹ R², NHSO₂R¹, OR¹, OCOR¹, OSO₂ R¹, SR¹, SOR¹, SO₂ R¹, SO₂ OR¹, SO₂ NR¹ R², COR¹,CR¹ ═NOR², CHR¹ CO₂ R², CO₂ R¹, CONR¹ R², CSNR¹ R², CH₃ O₂ C.C:CH.OCH₃,1-(imidazol-1-yl)vinyl, a 5-membered heterocyclic ring containing one,two or three nitrogen heteroatoms, or a 5- or 6-membered heterocyclicring containing one or two oxygen or sulphur heteroatoms, optionally anitrogen heteroatom and optionally one or two oxo or thioxosubstituents; or X and Y, when ortho to one another, join to form a 5-or 6-membered aliphatic or aromatic ring optionally containing one ortwo oxygen, sulphur or nitrogen atoms or one, two or three nitrogenatoms; A, B, D, E, G, U and V are independently hydrogen, halogen(especially fluorine and chlorine), C₁₋₄ alkyl (especially methyl), C₁₋₄alkoxy (especially methoxy), cyano, nitro or trifluoromethyl; and R¹ andR² are independently hydrogen, C₁₋₄ alkyl, C₂₋₄ alkenyl or phenyl; thealiphatic moieties of any of the foregoing being optionally substitutedwith one or more of halogen, cyano, OR¹, SR¹, NR¹ R², SiR¹ ₃ or OCOR¹and the phenyl moieties of any of the foregoing being optionallysubstituted with one or more of halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, nitroor cyano.

Because of the unsymmetrically substituted double bond of the propenoategroup, the compounds of the invention may be obtained in the form ofmixtures of (E) and (Z) geometric isomers. However, these mixtures canbe separated into individual isomers, and this invention embraces suchisomers and mixtures thereof in all proportions including those whichconsist substantially of the (Z)-isomer and those which consistsubstantially of the (E)-isomer.

The (E)-isomer, in which the groups --CO₂ CH₃ and --OCH₃ are on oppositesides of the olefinic bond of the propenoate group, are the morefungicidally active and form a preferred embodiment of the invention.

Alkyl groups contain from 1 to 4 carbon atoms and may be in the form ofstraight or branched chains. Examples are methyl, ethyl, iso-propyl,n-butyl and t-butyl. Cycloalkyl groups contain from 3 to 6 carbon atomsand include cyclopropyl and cyclohexyl.

Alkenyl and alkynyl groups contain from 2 to 4 carbon atoms and may bein the form of straight or branched chains. Examples are ethenyl, allyl,methylallyl and propargyl.

Halogen is typically fluorine, chlorine or bromine.

Substituted aliphatic moieties include, in particular, halo(C₁₋₄)alkyl,halo(C₁₋₄)alkoxy, halo(C₁₋₄)alkylthio, CH₂ OR¹, CH₂ SR¹ and CH₂ NR¹ R²,wherein R¹ and R² are H, C₁₋₄ alkyl or phenyl.

Typical optional substituents of phenyl moieties are fluorine, chlorine,methyl, methoxy, nitro and cyano. The ring ##STR3## in formula (I) is apyrimidine ring which may be joined to the phenoxy groups by any two ofits ring carbon atoms adjacent to a ring nitrogen atom. Of particularinterest are those compounds of formula (I) in which K and L are bothnitrogen and M is CH. Typically, one or both of X and Y are hydrogen.When one of X and Y is not hydrogen it is preferably attached to the2-position of the phenyl ring.

Thus, in one aspect, the invention provides compounds of formula (I) inwhich K, L and M have the meanings previously given; X, which ispreferably attached to the 2-position of the phenyl ring, is hydrogen,halogen (e.g. fluorine, chlorine or bromine), C₁₋₄ alkyl (e.g. methyl orethyl), C₁₋₄ alkyl (especially methyl) substituted with halogen (e.g.fluorine, chlorine or bromine), hydroxy, cyano, C₁₋₄ alkoxy (e.g.methoxy) or C₁₋₄ alkanoyloxy (e.g. acetoxy), C₂₋₄ alkenyl (e.g. ethenyl,allyl or methylallyl), C₂₋₄ alkynyl (e.g. ethynyl or propargyl), C₂₋₄alkenyloxy (e.g. allyloxy), C₂₋₄ alkynyloxy (e.g. propargyloxy), phenyl,benzyl, cyano, isocyano thiocyanato, isothiocyanato, nitro, amino, mono-or di(C₁₋₄)alkylamino (e.g. methylamino or dimethylamino), formylamino,C₁₋₄ alkanoylamino (e.g. acetamido), benzoylamino, ureido, phenylureido,C₁₋₄ alkylsulphonylamino (e.g. mesylamino), phenylsulphonylamino,hydroxy, C₁₋₄ alkoxy (e.g. methoxy or ethoxy), phenoxy, C₁₋₄ alkanoyloxy(e.g. acetoxy), C₁₋₄ alkylsulphonyloxy (e.g. mesyloxy),phenylsulphonyloxy, C₁₋₄ alkylthio (e.g. methylthio), C₁₋₄alkylsulphinyl (e.g. methylsulphinyl), C₁₋₄ alkylsulphonyl (e.g. mesyland n-butylsulphonyl), formyl, C₁₋₄ alkanoyl (e.g. acetyl), benzoyl,hydroxyimino(C₁₋₄)alkyl (e.g. hydroxyiminomethyl), C₁₋₄alkoxyimino(C₁₋₄)alkyl (e.g. methoxyiminomethyl), carbamoyl, C₁₋₄alkylcarbamoyl (e.g. methylcarbamoyl), thiocarbamoyl or C₁₋₄alkylthiocarbamoyl (e.g. methylthiocarbamoyl), the phenyl ring of any ofthe foregoing being optionally substituted with halogen (e.g. fluorineor chlorine), C₁₋₄ alkyl (e.g. methyl), C₁₋₄ alkoxy (e.g. methoxy),nitro or cyano; and Y is halogen (e.g. fluorine or chlorine), C₁₋₄ alkyl(e.g. methyl), C₁₋₄ alkoxy (e.g. methoxy), nitro, cyano or preferably,hydrogen, or X and Y, when ortho to one another, together formmethylenedioxy, or together with the phenyl ring to which they areattached form a naphthalene, quinoline, benzimidazole or benzothienylring.

In another aspect the invention provides compounds of the formula (I.1):##STR4## in which X is hydrogen, halogen (especially chlorine), C₁₋₄alkyl (especially methyl), C₁₋₄ alkoxy (especially methoxy),trifluoromethyl, cyano, thiocarbamoyl or nitro, and Y is hydrogen orfluoro.

The invention is illustrated by the compounds listed in Tables I to IIIwhich follow. Throughout these Tables the methyl 3-methoxypropenoategroup has the (E)-configuration and the substituents E, G, U and V areall hydrogen.

                  TABLE I                                                         ______________________________________                                         ##STR5##                                                                     Com-                            Melting                                       pound                           point  Ole-                                   No.   X               Y         (°C.)                                                                         finic*                                 ______________________________________                                         1    H               H         glass  7.46                                    2    2-F             H         gum    7.47                                    3    3-F             H         gum    7.47                                    4    3-F             H         87-9   7.46                                    5    2-Cl            H         glass  7.38                                    6    3-Cl            H                                                        7    4-Cl            H                                                        8    2-Br            H         glass  7.42                                    9    2-Cyano         H         118-119                                                                              7.50                                    10   3-Cyano         H         gum    7.49                                    11   4-Cyano         H         gum    7.49                                    12   2-Isocyano      H                                                        13   2-NO.sub.2      H         120-121                                                                              752                                     14   3-NO.sub.2      H         gum    7.49                                    15   4-NO.sub.2      H         gum    7.48                                    16   2-NH.sub.2      H         gum    7.46                                    17   3-NH(CH.sub.3)  H                                                        18   2-N(CH.sub.3).sub.2                                                                           H                                                        19   2-NH.CHO        H                                                        20   2-NH.COCH.sub.3 H                                                        21   3-NH.COC.sub.6 H.sub.5                                                                        H                                                        22   2-NH.CONH.sub.2 H                                                        23   3-NH.CONH(C.sub.2 H.sub.5)                                                                    H                                                        24   2-NH.SO.sub.2 CH.sub.3                                                                        H                                                        25   3-NH.SO.sub.2 C.sub.6 H.sub.5                                                                 H                                                        26   2-OH            H         159-161                                                                              7.45                                    27   3-OH            H                                                        28   4-OH            H                                                        29   2-OCH.sub.3     H         gum    7.49                                    30   3-OCH.sub.3     H         gum    7.47                                    31   4-OCH.sub.3     H         88-90  7.45                                    32   2-OC.sub.2 H.sub.5                                                                            H         glass  7.46                                    33   3-(2-FC.sub.6 H.sub.4 O)                                                                      H                                                        34   2-OCOCH.sub.3   H         gum    7.47                                    35   2-OSO.sub.2 CH.sub.3                                                                          H         foam   7.47                                    36   3-(4-CH.sub.3 C.sub.6 H.sub.4 SO.sub.2 O)                                                     H                                                        37   2-SCN           H                                                        38   3-SCN           H                                                        39   4-SCN           H                                                        40   2-SCH.sub.3     H         gum    7.48                                    41   3-SCH.sub.3     H                                                        42   4-SCH.sub.3     H                                                        43   2-S(O)CH.sub.3  H         135-6  7.48                                    44   2-SO.sub.2 CH.sub.3                                                                           H         61-4   7.49                                    45   4-SO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                          H                                                        46   2-CHO           H         foam   7.50                                    47   3-CHO           H                                                        48   4-CHO           H                                                        49   2-COCH.sub. 3   H         99-101 7.42                                    50   3-COC.sub.6 H.sub.5                                                                           H                                                        51   2-( .sub.--E)CH:NOH                                                                           H         146-7  7.45                                    52   3-( .sub.--E)CH:NOH                                                                           H                                                        53   4-( .sub.--E)CH:NOH                                                                           H                                                        54   2-( .sub.--E)CH:NOCH.sub.3                                                                    H                                                        55   2-( .sub.--E)C(CH.sub.3):NOH                                                                  H                                                        56   2-CONH.sub.2    H                                                        57   3-CONH(CH.sub.3)                                                                              H                                                        58   4-CON(CH.sub.3).sub.2 H                                                  59   2-CSNH.sub.2    H         131-3  7.49                                    60   2-CSNH(CH.sub.3)                                                                              H                                                        61   2-CH.sub.3      H         gum    7.48                                    62   3-CH.sub.3      H         92-5   7.45                                    63   4-CH.sub.3      H         gum    7.46                                    64   2-C.sub.2 H.sub.5                                                                             H         60-2   7.47                                    65   2-CH.sub.2 F    H                                                        66   2-CH.sub.2 Br   H                                                        67   2-CH.sub.2 Cl   H                                                        68   2-CH.sub.2 CN   H                                                        69   2-CH.sub.2 OH   H                                                        70   2-CH.sub.2 OCH.sub.3                                                                          H                                                        71   2-CH.sub.2 OCOCH.sub.3                                                                        H                                                        72   3-CH.sub.2 CN   H                                                        73   4-CH.sub.2 OH   H                                                        74   3-CH.sub.2 OCH.sub.3                                                                          H                                                        75   2-CH:CH.sub.2   H                                                        76   2-CH.sub.2 CH:CH.sub.2                                                                        H         gum    7.47                                    77   2-C CH          H         66-8   7.46                                    78   2-CH.sub.2 C CH H                                                        79   3-CH.sub.2 C(CH.sub.3):CH.sub.2                                                               H                                                        80   2-OCH.sub.2 CH:CH.sub.2                                                                       H         glass  7.47                                    81   2-OCH.sub.2 C CH                                                                              H         gum    7.47                                    82   2-C.sub.6 H.sub.5                                                                             H         55     7.40                                    83   3-C.sub.6 H.sub.5                                                                             H                                                        84   4-C.sub.6 H.sub.5                                                                             H                                                        85   2-C.sub.6 H.sub.5 O                                                                           H                                                        86   3-C.sub.6 H.sub.6 O                                                                           H                                                        87   4-C.sub.6 H.sub.5 O                                                                           H                                                        88   2-(4-ClC.sub.6 H.sub.4 O)                                                                     H                                                        89   2-C.sub.6 H.sub.5 CH.sub.2 O                                                                  H                                                        90   2-Cyano         4-Cl                                                     91   2-NO.sub.2      4-F                                                      92   2-Cl            4-Cl                                                     93   2-OCH.sub.3     3-OCH.sub.3                                              94   2-Cyano         5-Cl                                                     95   2-Cyano         6-Cyano                                                  96   2-F             5-Cl                                                     97   3-OCH.sub.3     5-OCH.sub.3                                              98   3-Cyano         4-F                                                      99   2-NO.sub.2      3-OCH.sub.3                                             100   3-OCH.sub.3     5-Cyano                                                 101   2-CO.sub.2 CH.sub.3                                                                           H         glass  7.50                                   102   2-I             H         glass  7.48                                   103   2-CF.sub.3      H         99-101 7.48                                   104   2- .sub.-i-C.sub.3 H.sub.7                                                                    H         63- 5  74.7                                   105   2- .sub.-i-C.sub.2 H.sub.7 O                                                                  H         glass  7.47                                   106   2-F             6-F       87-8   74.9                                   107   2-F             4-F       92-4   7.48                                   108   2-F             3-F       gum    7.48                                   109   2- -n-C.sub.2 H.sub.7 O                                                                       H         gum    7.46                                   110   2- -n-C.sub.4 H.sub.9 O                                                                       H         gum    7.47                                   111   2-CH(OH)CH.sub.3                                                                              H         50-3   74.6                                   112   2- .sub.-t-C.sub.4 H.sub.9                                                                    H         gum    7.47                                   113   2- .sub.-s-C.sub.4 H.sub.9                                                                    H         gum    7.47                                   114   2- -n-C.sub.3 H.sub.7                                                                         H         gum    7.47                                   115   2-( .sub.--E/ .sub.--Z)-CHCH(CH.sub.3)                                                        H         glass  .sup. 7.46.sup.1                       116   2-Cyano         4-OCH.sub.3                                                                             gum    7.50                                   117   2-Cyano         5-OCH.sub.3                                                                             oil    7.50                                   118   2-Cyano         4-Cl      78-82  75.0                                   119   2-Cyano         5-N(C.sub.2 H.sub.5).sub.2                                                              oil    7.50                                   120   2-CONH.sub.2    H         138-151                                                                              7.46                                   121   2-C CSi(CH.sub.3).sub.3                                                                       H         gum    7.46                                   122   2-F             5-F       100-101                                                                              7.48                                   123   2-( .sub.--E)-  H         130-131                                                                              7.45                                         CH.sub.3 O.sub.2 C.C:CH.OCH.sub.3                                       124   3-F             5-F       68-70  7.47                                   125   2-NHOH          H                                                       126   2-CH.sub.2 OCH.sub.3                                                                          H                                                       127   2-CH.sub.2 CN   H                                                       128   2-N.sub.3 H                                                             129   2-Cyano         6-F                                                     130   2-NO.sub.2      6-F                                                     131   2-CSNH.sub.2    6-F                                                     132   2-Cyano         3-F                                                     133   2-Cyano         5-F                                                     134   2-Cyano         3-OCH.sub.3                                             135   2-Cyano         6-OCH.sub.3                                             136   2-NO.sub.2      4-OCH.sub.3                                             137   2-NO.sub.2      5-OCH.sub.3                                             138   2-NO.sub.2      6-OCH.sub.3                                             139   2-CSNH.sub.2    3-OCH.sub.3                                             140   2-CSNH.sub.2    4-OCH.sub.3                                             141   2-CSNH.sub.2    5-OCH.sub.3                                             142   2-CSNH.sub.2    6-OCH.sub.3                                             143   2-Cyano         3-Cyano                                                 144   2-F             3-Cyano                                                 144   2-OCH.sub.3     3-Cyano                                                 145   3-Cyano         6-F                                                     146                                                                                  ##STR6##       H                                                       147                                                                                  ##STR7##       H                                                       148                                                                                  ##STR8##       H                                                       149                                                                                  ##STR9##       H                                                       150   2-Cyano         4-Br                                                    151   2-Cyano         6-Br                                                    152   2-Cyano         4-NO.sub.2                                              153   2-Cyano         6-NO.sub.2                                              154   2-Cyano         6-OC.sub.2 H.sub.5                                      155   2-Cyano         4-CO.sub.2 CH.sub.3                                     156   2-Cyano         6-CO.sub.2 C.sub.2 H.sub.5                              157   2-Cyano         6-CH.sub.3                                              158   2-Cyano         5-CH.sub.2 C.sub.6 H.sub.5                              159   2-Cyano         4-OCF.sub.3                                             160   2-Cyano         4-Cyano                                                 ______________________________________                                         ##STR10##                                                                    Com-                        Melting                                           pound                       point    Ole-                                     No.   Ar                    (°C.)                                                                           finic*                                   ______________________________________                                        161                                                                                  ##STR11##            133-5    7.52                                     162                                                                                  ##STR12##                                                              163                                                                                  ##STR13##                                                              164                                                                                  ##STR14##                                                              165                                                                                  ##STR15##                                                              166                                                                                  ##STR16##                                                              167   Pentafluorophenyl                                                       168   2,4,6-Tri-FC.sub.6 H.sub.2                                              169   2,3,5,6-Tetra-FC.sub.6 H                                                170   2,3,6-Tri-FC.sub.6 H.sub.2                                              171   2,3-Di-cyano-6-FC.sub.6 H.sub.2                                         172   2,6-Di-F-3-CH.sub.3 OC.sub.6 H.sub.2                                    173   2,6-Di-F-4-CH.sub.3 OC.sub.6 H.sub.2                                    174   2,6-Di-F-3-NO.sub.2 OC.sub.6 H.sub.2                                    175   2,6-Di-F-4-NO.sub.3 OC.sub.6 H.sub.2                                    176   2,6-Di-F-3,5-di-CH.sub.3 OC.sub.6 H                                     177   4,6-Di-Br-2-cyano-C.sub.6 H.sub.2                                       178   3-Cyano-2,6-di-FC.sub.6 H.sub.2                                         179   6-Br-2-cyano-4-CH.sub.3 OC.sub.6 H.sub.2                                180   6-Br-4-Cl-2-cyano-C.sub.6 H.sub.2                                       181   6-B4-2-cyano-4-NO.sub.2 C.sub.6 H.sub.2                                 182   3-Br-2-cyano-6-CH.sub.3 OC.sub.6 H.sub.2                                183   3,6-Di-Cl-2-cyano-C.sub.6 H.sub.2                                       184   4,6-Di-Cl-2-cyano-C.sub.6 H.sub.2                                       185   3-Br-2-cyano-4-CH.sub.3 OC.sub.6 H.sub.2                                186   4-Br-2-cyano-6-NO.sub.2 C.sub.6 H.sub.2                                 187   4-Br-2-cyano-6-CH.sub.3 OC.sub.6 H.sub.2                                188   2-Cyano-4-I-6-CH.sub.3 OC.sub.6 H.sub.2                                 189   2-Cyano-6-CH.sub.2 O-4-NO.sub.2 C.sub.6 H.sub.2                         190   2-Cyano-4,6-di-NO.sub.2 C.sub.6 H.sub.2                                 191   2-Cyano-4-CH.sub.3 -6-NO.sub.2 C.sub.6 H.sub.2                          192   2-Cyano-4-CH.sub.3)-6-NO.sub.2 C.sub.6 H.sub.2                          193   2-Cyano-5,6-di-CH.sub.3 OC.sub.6 H.sub.2                                194   2-Cyano-5,6-di-CH.sub.3 O-3-CH.sub.3 C.sub.6 H                          195   3,4-Di-Br-2-cyano-6-CH.sub.3 OC.sub.6 H                                 196   3-Br-2-cyano-6-CH.sub.3 O-4-NO.sub.2C.sub.6 H                           197   2-Cyano-6-CH.sub.3 CH.sub.2 O-4-NO.sub.2 C.sub.6 H.sub.2                198                                                                                  ##STR17##                                                              199                                                                                  ##STR18##                                                              ______________________________________                                         *Chemical shift of signlet from olefinic proton on betamethoxypropenoate      group (ppm from tetramethylsilane). Solvent: CDCl.sub.3 unless otherwise      stated.                                                                       .sup.1 The ratio of the (E) and (Z)isomers of the prop1-enyl group of         compound No. 115 is either 2:1 or 1:2.                                   

                  TABLE II                                                        ______________________________________                                         ##STR19##                                                                    Table II comprises 199 compounds of the general structure above               with all the values of X and Y listed in Table I. That is,                    compound numbers 1 to 199 of Table II are the same as those of                Table I except that the pyrimidine ring is 4,6-disubstituted in               Table I and 2,4-disubstituted as shown in Table II.                           Com-                                                                          pound                         Melting                                         No    X                 Y     Point (°C.)                                                                    Olefinic*                               ______________________________________                                         1    H                 H     114-115 7.46                                    123   2-( .sub.--E)-CH.sub.3 O.sub.2 C.C:CH.OCH.sub.3                                                 H     60-70   and 7.47                                ______________________________________                                         *Chemical shift of singlet from olefinic proton on betamethoxypropenoate      group (ppm from tetramethylsilane). Solvent: CDCl.sub.3 unless other          stated.                                                                  

                  TABLE III                                                       ______________________________________                                         ##STR20##                                                                    Table III comprises 199 compounds of the general structure above              with all the values of X and Y listed in Table I. That is,                    compounds numbers 1 to 199 of Table III are the sames as those                of Table I except that the pyrimidine ring is 4,6-disubstituted in            Table I and 2,4-disubstituted as shown in Table III.                          Compound                    Melting                                           No.        X        Y       Point (°C.)                                                                    Olefinic*                                 ______________________________________                                        1          H        H       96-97   7.42                                      9          2-Cyano  H       foam    7.43                                      ______________________________________                                         *Chemical shift of singlet from olefinic proton on betamethoxypropenoate      group (ppm from tetramethylsilane). Solvent: CDCl.sub.3 unless other          stated.                                                                  

                  TABLE IV                                                        ______________________________________                                        Selected proton NMR data                                                      ______________________________________                                        Table IV shows selected proton NMR data for certain                           compounds described in Table I (except where otherwise                        indicated). Chemical shifts are measured in ppm from                          tetramethylsilane, and deuterochloroform was used as                          solvent. Unless otherwise stated, spectra were recorded                       on an instrument operating at 270 MHz. The following                          abbreviations are used:                                                                S = singlet                                                                   d = doublet                                                                   t = triplet                                                                   m = multiplet                                                                 q = quartet                                                                   dd = double doublet                                                           br = broad                                                                    ppm = parts by million                                               ______________________________________                                        Compound No  Proton NMR data                                                  ______________________________________                                        1            3.60(3H, s); 3.75(3H, s); 6.23(1H, s);                                        7.10-7.50(9H, m); 7.46(1H, s);                                                8.43(1H, s)ppm                                                   2            3.60(3H, s); 3.74(3H, s); 6.32(1H, s);                                        7.15-7.46(8H, m); 7.47(1H, s);                                                8.40(1H, s)ppm                                                   3            3.63(3H, s); 3.76(3H, s); 6.27(1H, s);                                        6.86-7.03(3H, m); 7.16-7.50(5H,                                               m); 7.47(1H, s); 8.43(1H, s)ppm                                  5            3.50(3H, s); 3.61(3H, s); 6.21(1H, s);                                        7.08-7.43(8H, m); 7.38(1H, s); 8.30(1H,                                       s)ppm                                                            8            3.54(3H, s); 3.68(3H, s); 6.23(1H,                                            s); 7.06-7.36(7H, m); 7.42(1H,                                                s); 7.59(1H, d); 8.33(1H, s)ppm                                  10           3.63(3H, s); 3.77(3H, s); 6.33(1H,                                            s); 7.20(1H, d); 7.25-7.60(7H,                                                m); 7.49(1H, s); 8.40(1H, s)ppm                                  11           3.62(3H, s); 3.78(3H, s); 6.34(1H,                                            s); 7.20(1H, d); 7.25-7.45(5H,                                                m), 7.49(1H, s); 7.73(2H, d);                                                 8.41(1H, s)ppm                                                   14           3.65(3H, s); 3.78(3H, s); 6.37(1H,                                            s); 7.08-7.65(6H, m); 7.49(1H,                                                s); 8.04(1H, t); 8.14(1H, dd);                                                8.41(1H, s)ppm                                                   15           3.64(3H, s); 3.78(3H, s);                                                     6.39(1H, s); 7.20(1H, d);                                                     7.26-7.46(5H, m); 7.48(1H, s);                                                8.32(2H, d); 8.42(1H, s)ppm                                      16           3.60(3H, s); 3.74(3H, s); 3.74(2H,                                            br s); 6.23(1H, s); 6.77-6.87(2H, m);                                         6.98-7.12(2H, m); 7.24-7.42(4H, m);                                           7.46(1H, s); 8.44(1H, s)ppm                                      30           3.61(3H, s); 3.76(3H, s); 3.82(3H,                                            s); 6.23(1H, s); 6.68-6.75(2H,                                                m); 6.80(1H, dd); 7.19(1H, d);                                                7.25-7.42(4H, m); 7.47(1H, s); 8.43(1H,                                       s)ppm                                                            32           1.23(3H, t); 3.59(3H, s); 3.73(3H,                                            s); 4.02(2H, q); 6.25(1H, s);                                                 7.00(2H, d); 7.46(1H, s); 8.39(1H,                                            s)ppm                                                            34           2.17(3H, s); 3.60(3H, s); 3.75(3H,                                            s); 6.29(1H, s); 7.18-7.43(8H,                                                m); 7.47(1H, s); 8.41(1H, s)ppm                                  35           3.12(3H, s); 3.61(3H, s); 3.74(3H,                                            s); 6.29(1H, s); 7.19-7.50(8H,                                                m); 7.47(1H, s); 8.40(1H, s)ppm                                  40           3.60(3H, s); 3.75(3H, s); 6.28(1H,                                            s); 7.09(1H, dd); 7.20-7.44(7H,                                               m); 7.48(1H, s); 8.42(1H, s)ppm                                  46           3.63(3H, s); 3.77(3H, s); 6.39(1H,                                            s); 7.20-7.45(6H, m); 7.50(1H,                                                s); 7.68(1H, t); 7.97(1H,                                                     d); 8.39(1H, s)ppm                                               61           2.17(3H, s); 3.60(3H, s); 3.75(3H,                                            s); 6.20(1H, s); 7.00-7.50(8H,                                                m); 7.48(1H, s); 8.42(1H, s)ppm                                  63           2.37(3H, s); 3.59(3H, s); 3.73(3H,                                            s); 6.22(1H, s); 7.00(2H, d);                                                 7.14-7.44(6H, m); 7.46(1H, s);                                                8.42(1H, s)ppm                                                   76           3.28-3.30(2H, d); 3.60(3H, s); 3.74(3H,                                       s); 4.98-5.02(1H, m); 5.05(1H,                                                s); 5.81-5.96(1H, m); 6.21(1H,                                                s); 7.04-7.08(1H, m); 7.18-7.42(7H,                                           m); 7.47(1H, s); 8.42(1H, s)ppm.                                 80           3.59(3H, s); 3.73(3H, s); 4.51-4.53(2H,                                       m); 5.16-5.26(2H, m); 5.79-5.94(1H,                                           m); 6.25(1H, s); 6.98-7.03(2H,                                                m); 7.12-7.42(6H, m); 7.47(1H,                                                s); 8.39(1H, s)ppm                                               81           2.48-2.50(1H, m); 3.60(3H, s);                                                3.74(3H, s); 3.65(2H, d);                                                     6.24(1H, s); 7.03-7.43(8H, m);                                                7.47(1H, s); 8.40(1H, s)ppm                                      101          3.62(3H, s); 3.75(3H, s); 3.76(3H,                                            s); 6.33(1H, s); 7.17-7.45(6H,                                                m); 7.50(1H, s); 7.57(1H, t);                                                 8.03(1H, d); 8.36(1H, s)ppm                                      102          3.62(3H, s); 3.76(3H, s); 6.31(1H,                                            s); 7.02(1H, t); 7.14-7.51(6H,                                                m); 7.48(1H, s); 7.88(1H, d);                                                 8.41(1H, s)ppm                                                   105          1.21(6H, d); 3.60(3H, s); 3.74(3H,                                            s); 4.44-4.56(1H, m); 6.23(1H, s);                                            6.95-7.02(2H, m); 7.11-7.49(6H, m);                                           7.47(1H, s)ppm                                                   106          3.62(3H, s); 3.74(3H, s); 6.38(1H,                                            s); 7.00(2H, t); 7.15-7.45(5H, m);                                            7.49(1H, s); 8.39(1H, s)ppm                                      108          3.62(3H, s); 3.74(3H, s); 6.35(1H,                                            s); 6.95-7.43(7H, m); 7.48(1H,                                                s); 8.39(1H, s)ppm                                               109          0.80(3H, t); 1.56-1.70(2H, m);                                                3.60(3H, s); 3.74(3H, s); 3.90(2H,                                            t); 6.24(1H, s); 6.98(2H, d);                                                 7.10-7.42(6H, m); 7.46(1H, s);                                                8.39(1H, s)ppm                                                   110          0.86(3H, t); 1.18-1.30(2H, m);                                                1.56-1.64(2H, m); 3.60(3H, s); 3.74(3H,                                       s); 3.94(2H, t); 6.25(1H, s);                                                 7.00(2H, d); 7.11-7.43(6H, m);                                                7.47(1H, s); 8.38(1H, s)ppm                                      112          1.34(9H, s); 3.68(3H, s); 3.74(3H,                                            s); 6.24(1H, s); 6.95-7.98(1H, m);                                            7.17-7.48(7H, m); 7.47(1H, s); 8.45(1H,                                       s)ppm                                                            113          0.79(3H, t); 1.16(3H, d); 1.49-1.67(2H,                                       m); 1.75-1.88(1H, m); 3.59(3H,                                                s); 3.74(3H, s); 6.19(1H, s); 7.00-7.05(1H,                                   m); 7.18-7.46(7H, m); 7.47(1H, s); 8.42(1H,                                   s)ppm                                                            114          0.91(3H, t); 1.53-1.66(2H, m);                                                2.49(2H, t); 3.59(3H, s); 3.74(3H,                                            s); 6.20(1H, s); 7.00-7.04(1H,                                                m); 7.18-7.46(7H, m); 7.47(1H,                                                s); 8.41(1H, s)ppm                                               115          For both isomers: 1.76-1.85(3H, m);                                           3.58(3H, s); 3.73(3H, s); 7.00-7.42(7H,                                       m); 7.46(1H, s); 7.54-7.58(1H,                                                m)ppm                                                                         For major isomer: 6.18(2/3H, s);                                              6.22-6.32(2/3H, m); 6.38(2/3H, br s);                                         8.42(2/3H, s)ppm. For minor isomer:                                           5.70-5.83(1/3H, m); 6.15(1/3H, s); - 6.44(1/3H,                               br s); 8.39(1/3H, s)ppm                                          116          3.63(3H, s); 3.75(3H, s); 3.85(3H,                                            s); 6.38(1H, s); 7.15-7.45(7H,                                                m); 7.50(1H, s); 8.40(1H, s)ppm                                  117          3.63(3H, s); 3.75(3H, s); 3.86(3H,                                            s); 6.40(1H, s); 6.80(1H, s);                                                 6.88(1H, d); 7.2-7.45(4H, m); 7.50(1H,                                        s); 7.61(1H, d); 8.41(1H, s)ppm                                  119          1.20(6H, t); 3.38(4H, q); 3.63(3H,                                            s); 3.74(3H, s); 6.35(1H, s);                                                 6.40(1H, d); 6.52(1H, dd); 7.2-7.46(5H,                                       m); 7.50(1H, s); 8.43(1H, s)ppm                                  121          0.10(9H, s); 3.61(3H, s); 3.74(3H,                                            s); 6.29(1H, s); 7.12-7.43(7H,                                                m); 7.46(1H, s); 7.50-7.55(1H,                                                m); 8.41(1H, s)ppm                                               9 (Table III)                                                                              3.57(3H, s); 3.68(3H, s); 6.75(1H,                                            d); 7.10-7.40(6H, m); 7.43(1H,                                                s); 7.59(1H, t); 7.68(1H, d);                                                 8.40(1H, d)ppm                                                   ______________________________________                                    

The compounds of the invention of formula (I) [equivalent to (IA) when Wis the group CH₃ O₂ C.C═CH.OCH₃ ] can be prepared by the stepsillustrated in Schemes I and II. Throughout these Schemes the terms X,Y, A, B, D, G, U, V, K, L and M are as defined above; W is CH₃ O₂C.C═CH.OCH₃ (or a group that can be transformed into CH₃ O₂ C.C═CH.OCH₃using methods previously described in EP-A-0242081); Z¹ and Z², whichmay be the same or different, are leaving groups (such as halogen or CH₃SO₂ --), Z¹ being the leaving group which is more readily displaced ifboth Z¹ and Z² are present in the same compound of if Z¹ and Z² are bothpresent in different compounds of a coupling reaction; T¹ is hydrogen ora metal (such as sodium); and T² is hydrogen, a metal (such as sodium)or a protecting group (such as benzyl). Each reaction shown in Schemes Iand II is performed either in a suitable solvent or without a solvent,and at a suitable temperature.

Thus compounds of the invention of formula [(IA): W is the group CH₃ O₂C.C═CH.OCH₃ ] can be prepared by two successive reactions of the Ullmanntype, using appropriately functionalised benzene and pyrimidineintermediates. The pathways shown in Schemes I and II illustrate that(i) the order of the steps by which these benzene and pyrimidine unitsare assembled can be varied; and (ii) the functional groups which reactduring the Ullmann coupling, namely an oxygen nucleophile and a leavinggroup on an aromatic ring, may be positioned on either of the substratesat each individual step.

For example, compounds of formula (IA) can be prepared from compounds offormula (II) by treatment with phenols of formula (III), wherein T¹ ishydrogen, in the presence of a base (such as potassium carbonate).Alternatively, compounds of formula (IA) can be prepared from compoundsof formula (II) by treatment with phenolate salts of formula (III),wherein T¹ is a metal (such as sodium).

Compounds of formula (II) can be prepared by treatment of compounds offormula (IV) with phenols of formula (V), wherein T¹ is hydrogen, in thepresence of a base (such as potassium carbonate). Alternatively,compounds of formula (II) can be prepared by treatment of compounds offormula (IV) with phenolate salts of formula (V), wherein T¹ is a metal(such as sodium). Similarly, compounds of formula (II) can be preparedby allowing compounds of formula (VI) to react with compounds of formula(VII); when T¹ is hydrogen, the reaction is performed in the presence ofa base (such as potassium carbonate).

The preparation of compounds of formula (IA) from intermediates (VIII),(XI) and (XII), as well as the preparation of these intermediates fromthe monocyclic precursors, is carried out by similar methods.

Modifications to the group W may be made at any appropriate stage in thepathways shown in Schemes I and II. For example, during one or more ofthe Ullmann couplings, W may be the group CH₂ CO₂ R (wherein R is H, CH₃or a metal) to be converted at the last stages of the synthesis into thegroup CH₃ O₂ C.C═CH.OCH₃ using, for example, one of the methodsdescribed in EP-A-0242081. When T² is a protecting group, it may beremoved at any appropriate reaction step. The substituents X, Y, A, B,D, E (one of K, L and M having the value CE, wherein E is as definedabove), G, U and V may also be modified at any appropriate reactionstep. For example, if X is NO₂ it may be converted via reduction anddiazotisation into a halogen, CN or OH group, and this may be carriedout on intermediates such as (XI) or (XII) or on the compounds offormula (IA). Or, for example, if G is a halogen such as chlorine, itmay be removed at an appropriate stage of the synthesis (such as at thelast stage) to give the corresponding pyrimidine in which G is hydrogen.

The intermediates of formulae (II) and (VIII) may be interconvertedusing standard methods. The intermediates of formulae (XI) and (XII) aresimilarly interconvertible. Compounds of formulae (III), (IV), (VI),(IX), (X), (XIII), (XIV), (XV), (XVI) and (XVII) can be prepared bystandard methods described in the chemical literature. Compounds offormulae (V) and (VII) can either be prepared by standard methodsdescribed in the chemical literature, or, when W is CH₃ O₂ C.C═CH.OCH₃,can be prepared by methods described in EP-A-0242081 and EP-A-0178826respectively. ##STR21##

In a further aspect, the invention provides processes as hereindescribedfor preparing the compounds of the invention.

The compounds of the invention are active fungicides and may be used tocontrol one or more of the following pathogens:

Pyricularia oryzae on rice.

Puccinia recondita, Puccinia striiformis and other rusts on wheat,Puccinia hordei, Puccinia striiformis and other rusts on barley, andrusts on other hosts e.g. coffee, pears, apples, peanuts, vegetables andornamental plants. Erysiphe graminis (powdery mildew) on barley andwheat and other powdery mildews on various hosts such as Sphaerothecamacularis on hops, Sphaerotheca fuliginea on cucurbits (e.g. cucumber),Podosphaera leucotricha on apple and Uncinula necator on vines.

Helminthosporium spp., Rhynchosporium spp., Septoria spp., Pyrenophoraspp., Pseudocercosporella herpotrichoides and Gaeumannomyces graminis oncereals.

Cercospora arachidicola and Cercosporidium personata on peanuts andother Cercospora species on other hosts, for example, sugar beet,bananas, soya beans and rice.

Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables,vines and other hosts. Alternaria spp. on vegetables (e.g. cucumber),oil-seed rape, apples, tomatoes and other hosts.

Venturia inaequalis (scab) on apples.

Plasmopara viticola on vines.

Other downy mildews such as Bremia lactucae on lettuce, Peronospora spp.on soybeans, tobacco, onions and other hosts, Pseudoperonospora humulion hops and Pseudoperonospora cubensis on cucurbits. Phytophthorainfestans on potatoes and tomatoes and other Phytophthora spp. onvegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoaand other hosts.

Thanatephorus cucumeris on rice and other Rhizoctonia species on varioushosts such as wheat and barley, vegetables, cotton and turf.

Some of the compounds show a broad range of activities against fungi invitro. They may also have activity against various post-harvest diseasesof fruit (e.g. Penicillium digitatum and italicum and Trichoderma virideon oranges, Gloeosporium musarum on bananas and Botrytis cinerea ongrapes).

Further, some of the compounds may be active as seed dressings againstpathogens including Fusarium spp., Septoria spp., Tilletia spp., (bunt,a seed-borne disease of wheat), Ustilago spp. and Helminthosporium spp.on cereals, Rhizoctonia solani on cotton and Pyricularia oryzae on rice.

The compounds may have systemic movement in plants. Moreover, thecompounds may be volatile enough to be active in the vapour phaseagainst fungi on the plant.

The invention therefore provides a method of combating fungi whichcomprises applying to a plant, to a seed of a plant or to the locus ofthe plant or seed a fungicidally effective amount of a compound ashereinbefore defined, or a composition containing the same.

The compounds may be used directly for agricultural purposes but aremore conveniently formulated into compositions using a carrier ordiluent. The invention thus provides fungicidal compositions comprisinga compound as hereinbefore defined and an acceptable carrier or diluenttherefor.

The compounds can be applied in a number of ways. For example, they canbe applied, formulated or unformulated, directly to the foliage of aplant, to seeds or to other medium in which plants are growing or are tobe planted, or they can be sprayed on, dusted on or applied as a creamor paste formulation, or they can be applied as a vapour or as slowrelease granules.

Application can be to any part of the plant including the foliage,stems, branches or roots, or to soil surrounding the roots, or to theseed before it is planted, or to the soil generally, to paddy water orto hydroponic culture systems. The invention compounds may also beinjected into plants or sprayed onto vegetation using electrodynamicspraying techniques or other low volume methods.

The term "plant" as used herein includes seedlings, bushes and trees.Furthermore, the fungicidal method of the invention includespreventative, protectant, prophylactic and eradicant treatments.

The compounds are preferably used for agricultural and horticulturalpurposes in the form of a composition. The type of composition used inany instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dustable powders or granulescomprising the active ingredient (invention compound) and a soliddiluent or carrier, for example, fillers such as kaolin, bentonite,kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia,fuller's earth, gypsum, diatomaceous earth and china clay. Such granulescan be preformed granules suitable for application to the soil withoutfurther treatment. These granules can be made either by impregnatingpellets of filler with the active ingredient or by pelleting a mixtureof the active ingredient and powdered filler. Compositions for dressingseed may include an agent (for example, a mineral oil) for assisting theadhesion of the composition to the seed; alternatively the activeingredient can be formulated for seed dressing purposes using an organicsolvent (for example, N-methylpyrrolidone, propylene glycol ordimethylformamide). The compositions may also be in the form of wettablepowders or water dispersible granules comprising wetting or dispersingagents to facilitate the dispersion in liquids. The powders and granulesmay also contain fillers and suspending agents.

Emulsifiable concentrates or emulsions may be prepared by dissolving theactive ingredient in an organic solvent optionally containing a wettingor emulsifying agent and then adding the mixture to water which may alsocontain a wetting or emulsifying agent. Suitable organic solvents arearomatic solvents such as alkylbenzenes and alkylnaphthalenes, ketonessuch as cyclohexanone and methylcyclohexanone, chlorinated hydrocarbonssuch as chlorobenzene and trichlorethane, and alcohols such as benzylalcohol, furfuryl alcohol, butanol and glycol ethers.

Suspension concentrates of largely insoluble solids may be prepared byball or bead milling with a dispersing agent with a suspending agentincluded to stop the solid settling.

Compositions to be used as sprays may be in the form of aerosols whereinthe formulation is held in a container under pressure of a propellant,e.g. fluorotrichloromethane or dichlorodifluoromethane.

The invention compounds can be mixed in the dry state with a pyrotechnicmixture to form a composition suitable for generating in enclosed spacesa smoke containing the compounds.

Alternatively, the compounds may be used in microencapsulated form. Theymay also be formulated in biodegradable polymeric formulations to obtaina slow, controlled release of the active substance.

By including suitable additives, for example additives for improving thedistribution, adhesive power and resistance to rain on treated surfaces,the different compositions can be better adapted for various utilities.

The invention compounds can be used as mixtures with fertilisers (e.g.nitrogen-, potassium- or phosphorus-containing fertilisers).Compositions comprising only granules of fertiliser incorporating, forexample coated with, the compound are preferred. Such granules suitablycontain up to 25% by weight of the compound. The invention thereforealso provides a fertiliser composition comprising a fertiliser and thecompound of general formula (I) or a salt or metal complex thereof.

Wettable powders, emulsifiable concentrates and suspension concentrateswill normally contain surfactants, e.g. a wetting agent, dispersingagent, emulsifying agent or suspending agent. These agents can becationic, anionic or non-ionic agents.

Suitable cationic agents are quaternary ammonium compounds, for example,cetyltrimethylammonium bromide. Suitable anionic agents are soaps, saltsof aliphatic monoesters of sulphuric acid (for example, sodium laurylsulphate), and salts of sulphonated aromatic compounds (for example,sodium dodecylbenzenesulphonate, sodium, calcium or ammoniumlignosulphonate, butylnaphthalene sulphonate, and a mixture of sodiumdiisopropyl- and triisopropyl- naphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethyleneoxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkylphenols such as octyl- or nonylphenol and octylcresol. Other non-ionicagents are the partial esters derived from long chain fatty acids andhexitol anhydrides, the condensation products of the said partial esterswith ethylene oxide, and the lecithins. Suitable suspending agents arehydrophilic colloids (for example, polyvinylpyrrolidone and sodiumcarboxymethylcellulose), and swelling clays such as bentonite orattapulgite.

Compositions for use as aqueous dispersions or emulsions are generallysupplied in the form of a concentrate containing a high proportion ofthe active ingredient, the concentrate being diluted with water beforeuse. These concentrates should preferably be able to withstand storagefor prolonged periods and after such storage be capable of dilution withwater in order to form aqueous preparations which remain homogeneous fora sufficient time to enable them to be applied by conventional sprayequipment. The concentrates may conveniently contain up to 95%, suitably10-85%, for example 25-60%, by weight of the active ingredient. Afterdilution to form aqueous preparations, such preparations may containvarying amounts of the active ingredient depending upon the intendedpurpose, but an aqueous preparation containing 0.0005% or 0.01% to 10%by weight of active ingredient may be used.

The compositions of this invention may contain other compounds havingbiological activity, e.g. compounds having similar or complementaryfungicidal activity or which possess plant growth regulating, herbicidalor insecticidal activity.

A fungicidal compound which may be present in the composition of theinvention may be one which is capable of combating ear diseases ofcereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporiumspp., seed and soil-borne diseases and downy and powdery mildews ongrapes and powdery mildew and scab on apple, etc. By including anotherfungicide, the composition can have a broader spectrum of activity thanthe compound of general formula (I) alone. Further the other fungicidecan have a synergistic effect on the fungicidal activity of the compoundof general formula (I). Examples of fungicidal compounds which may beincluded in the composition of the invention are(RS)-1-aminopropylphosphonic acid,(RS)-4-(4-chlorophenyl)-2-phenyl-2-(1H-1,2,4-triazol-1-ylmethyl)butyronitrile,(RS)-4-chloro-N-(cyano(ethoxy)methyl)benzamide,(Z)-N-but-2-enyloxymethyl-2-chloro-2',6'-diethylacetanilide,1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea, 1-[(2RS, 4RS; 2RS,4RS)-4-bromo-2-(2,4-dichlorophenyl)tetrahydrofurfuryl]-1H-1,2,4-traizole,3-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)quinazolin-4(3H)-one,3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol-1-methyl)-1,3-dioxolan-2-yl]phenyl-4-chlorophenylether,4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulphonamide,4-chlorobenzylN-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)thioacetamidate,5-ethyl-5,8-dihydro-8-oxo(1,3)-dioxolo(4,5-g)quinoline-7-carboxylicacid,alpha-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-gamma-butyrolactone,anilazine, benalaxyl, benomyl, biloxazol, binapacryl, bitertanol,blasticidin S, bupirimate, buthiobate, captafol, captan, carbendazim,carboxin, chlorbenzthiazone, chloroneb, chlorothalonil, chlorozolinate,copper containing compounds such as copper oxychloride, copper sulphateand Bordeaux mixture, cycloheximide, cymoxanil, cyproconazole,cyprofuram, di-2-pyridyl disulphide 1,1'-dioxide, dichlofluanid,dichlone, diclobutrazol, diclomezine, dicloran, dimethamorph,dimethirimol, diniconazole, dinocap, ditalimfos, dithianon, dodemorph,dodine, edifenphos, etaconazole, ethirimol, ethyl(Z)-N-benzyl-N-([methyl(methylthioethylideneamino-oxycarbonyl)amino]-thio)-beta-alaninate,etridiazole, fenapanil, fenarimol, fenfuram, fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, flutolanil, flutriafol,fluzilazole, folpet, fosetyl-aluminium, fuberidazole, furalaxyl,furconazole-cis, guazatine, hexaconazole, hydroxyisoxazole, imazalil,iprobenfos, iprodione, isoprothiolane, kasugamycin, mancozeb, maneb,mepronil, metalaxyl, methfuroxam, metsulfovax, myclobutanil,N-(4-methyl-6-prop-1-ynylpyrimidin-2-yl)aniline, neoasozin, nickeldimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurance,organomercury compounds, oxadixyl, oxycarboxin, pefurazoate,penconazole, pencycuron, phenazin oxide, phthalide, polyoxin D, polyram,probenazole, prochloraz, procymidone, propamocarb, propiconazole,propineb, prothiocarb, pyrazophos, pyrifenox, pyroquilon, pyroxyfur,pyrrolnitrin, quinomethionate, quintozene, streptomycin, sulphur,techlofthalam, tecnazene, tebuconazole, tetraconazole, thiabendazole,thiophanatemethyl, thiram, tolclofos-methyl, triacetate salt of1,1'-iminodi(octamethylene)diguanidine, triadimefon, triadimenol,triazbutyl, tricyclazole, tridemorph, triforine, validamycin A,vinclozolin and zineb. The compounds of general formula (I) can be mixedwith soil, peat or other rooting media for the protection of plantsagainst seed-borne, soil-borne or foliar fungal diseases.

Suitable insecticides which may be incorporated in the composition ofthe invention include buprofezin, carbaryl, carbofuran, carbosulfan,chlorpyrifos, cycloprothrin, demeton-s-methyl, diazinon, dimethoate,ethofenprox, fenitrothion, fenobucarb, fenthion, formothion, isoprocarb,isoxathion, monocrotophos, phenthoate, pirimicarb, propaphos and XMC.

Plant growth regulating compounds are compounds which control weeds orseedhead, formation, or selectively control the growth of less desirableplants (e.g. grasses).

Examples of suitable plant growth regulating compounds for use with theinvention compounds are 3,6-dichloropicolinic acid,1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylicacid, methyl-3,6-dichloroanisate, abscisic acid, asulam,benzoylpropethyl, carbetamide, daminozide, difenzoquat, dikegulac,ethephon, fenpentezol, fluoridamid, glyphosate, glyphosine,hydroxybenzonitriles (e.g. bromoxynil), inabenfide, isopyrimol, longchain fatty alcohols and acids, maleic hydrazide, mefluidide,morphactins (e.g. chlorfluoroecol), paclobutrazol, phenoxyacetic acids(e.g. 2,4-D or MCPA), substituted benzoic acid (e.g. triiodobenzoicacid), substituted quaternary ammonium and phosphonium compounds (e.g.chloromequat, chlorphonium or mepiquatchloride), tecnazene, the auxins(e.g. indoleacetic acid, indolebutyric acid, naphthylacetic acid ornaphthoxyacetic acid), the cytokinins (e.g. benzimidazole,benzyladenine, benzylaminopurine, diphenylurea or kinetin), thegibberellins (e.g. GA₃, GA₄ or GA₇) and triapenthenol.

The following Examples illustrate the invention. In the Examples, theterm `ether` refers to diethyl ether, anhydrous magnesium sulphate wasused to dry solutions, and solutions were concentrated under reducedpressure. Reactions involving air- or water-sensitive intermediates wereperformed under an atmosphere of nitrogen and solvents were dried beforeuse, where appropriate. Unless otherwise stated, chromatography wasperformed on a column of silica gel as the stationary phase. NMR dataare selective; no attempt is made to list every absorption in all cases.¹ H NMR spectra were recorded using CDCl₃ -solutions on an instrumentoperating at 270 MHz, unless otherwise stated. The followingabbreviations are used:

DMSO=dimethylsulphoxide

DMF=N,N-dimethylformamide

NMR=nuclear magnetic resonance

IR=infrared

GC=Gas chromatography

TLC=Thin layer chromatography

s=singlet

d=doublet

m=multiplet

mp=melting point

ppm=parts per million

EXAMPLE 1

This example illustrates the preparation of (E)-methyl2-[2-(4-phenoxypyrimidin-2-yloxy)phenyl]-3-methoxypropenoate (compoundNo. 1 of Table III).

To a suspension of sodium hydride (0.3 g, 6.85 mmol, 50% dispersion inoil pre-washed with n-hexane) in dry DMF (4 ml) was added dropwise asolution of phenol (0.59 g, 6.23 mmol) in dry DMF (1 ml). The resultingmixture was stirred under an atmosphere of nitrogen until effervescencehad ceased. The resulting mixture was diluted with dry DMF (3 ml) andthen added dropwise to a stirred solution of4-chloro-2-methylthiopyrimidine (1.00 g, 6.23 mmol) in dry DMF (3 ml) at0° C. An exothermic reaction took place and the temperature of thereaction mixture rose to 5° C. After stirring under nitrogen for 30minutes at 10° C., GC analysis indicated the formation of a singleproduct (98.8%). The reaction mixture was diluted with water (15 ml) andextracted with ether (2×20 ml). The combined ether extracts were washedwith 5% sodium hydroxide solution (2×15 ml) and brine (15 ml) and thendried. Evaporation of the solvent gave 2-methylthio-4-phenoxypyrimidineas a pale yellow oil (1.40 g, 94% pure by GC) which was used directly inthe next stage. ¹ H NMR delta: 2.37(3H,s)ppm.

To a stirred solution of 2-methylthio-4-phenoxypyrimidine (1.00 g, 4.59mmol) in chloroform (15 ml) at -15° C. was added m-chloroperbenzoic acid(2.88 g, 9.17 mmol) in chloroform (35 ml). A white cloudy suspensionformed. The reaction mixture was allowed to warm to room temperature andstirring continued for four hours. GC analysis indicated the formationof a single product (95%). The reaction mixture was washed with asaturated aqueous solution of sodium sulphite (2×25 ml), saturatedsodium carbonate solution (2×25 ml) and water (25 ml). The chloroformsolution was separated and dried. The solvent was evaporated to give acolourless oil which crystallised on cooling and scratching to afford2-methanesulphonyl-4-phenoxypyrimidine as a white solid (1.05 g).Recrystallisation from chloroform:n-hexane gave a white finely dividedpowder, mp 113°-116° C., ¹ H NMR delta: 3.17 (3H,s)ppm; IR maxima(nujol) 1133, 1315 cm⁻¹.

To a solution of 2-methanesulphonyl-4-phenoxypyrimidine (200 mg, 0.80mmol) in dry DMF (2 ml) at 0° C. under an atmosphere of nitrogen wasadded anhydrous potassium carbonate (110 mg, 0.80 mmol). A solution of(E)-methyl 2-(2-hydroxyphenyl)-3-methoxypropenoate (166 mg, 0.80 mmol;prepared as described in Example 3 of EP-A-0242081) in dry DMF (1 ml)was then added dropwise with stirring. The reaction mixture was allowedto rise to room temperature and then stirred over the weekend. Themixture was diluted with water (15 ml) and then extracted with ether(2×20 ml). The combined ether extracts were washed with brine, dried andevaporated to give a yellow oil. Chromatography (eluent ether: n-hexane,5:1) gave a pale yellow cloudy oil, which on trituration with etherafforded the title compound as a white solid (0.10 g). Recrystallisationfrom ether:n-hexane gave a white solid (65 mg, 22% yield) mp 96°-7° C.;¹ H NMR delta: 3.57 (3H,s); 3.70 (3H,s); 6.48 (1H,d); 7.12-7.45 (9H,m);7.42 (1H,s); 8.29 (1H,d)ppm. IR maxima 1708, 1632 cm⁻¹.

EXAMPLE 2

This example illustrates the preparation of (E)-methyl2-[2-(2-phenoxypyrimidin-4-yloxyphenyl]-3-methoxypropenoate (compoundNo. 1 of Table II).

To a stirred solution of 4-chloro-2-methylthiopyrimidine (10.00 g, 62.3mmol) in glacial acetic acid (50 ml) at 10°-15° C. was added a solutionof potassium permanganate (12.50 g, 79.15 mmol) in water (100 ml). Thereaction mixture was stirred overnight at room temperature, cooled to 5°C. and then treated with gaseous sulphur dioxide until the dark solutionwas decolourised. Water was added and the mixture extracted withchloroform. The combined organic layers were washed with saturatedaqueous sodium bicarbonate solution and then water, and dried.Evaporation gave 4-chloro-2-methanesulphonylpyrimidine as a white solid(10.84 g), mp 91°-3° C. 4-Chloro-2-methanesulphonylpyrimidine (7.00 g,36.33 mmol) was treated with sodium phenoxide [from phenol (3.41 g,36.33 mmol) and sodium hydride (1.74 g, 39.97 mmol, 50% dispersion inoil)] in dry DMF (100 ml) at 0°-5° C. After 30 minutes, the startingmaterial had been consumed (GC analysis). The reaction mixture wasdiluted with water and then extracted with ether (×2). The combinedextracts were washed with 5% aqueous sodium hydroxide solution (×2) andbrine, and then dried. Evaporation of the solvent gave a very paleyellow, mobile oil (5.35 g). Chromatography (eluent ether:n-hexane, 2:3)followed by crystallisation afforded 4-chloro-2-phenoxypyrimidine as awhite solid (3.50 g, 84% pure by GC). Further chromatography yieldedpure product (2.50 g, 33%), mp 59°-60° C.

To a stirred solution of 4-chloro-2-phenoxypyrimidine (2.00 g, 9.68mmol) in dry DMSO (15 ml) and DMF (10 ml) at 10° C. under nitrogen wasadded dropwise a solution/suspension of sodium methanethiolate (0.77 g,9.68 mmol) in dry DMSO (15 ml) and DMF (5 ml). After approximately onehour below 15° C., the reaction mixture was diluted with water and thenextracted (×3) with ether. The combined ether extracts were washed withbrine and then dried. Evaporation of the solvent gave4-methylthio-2-phenoxypyrimidine as a thick, pale yellow oil (2.00 g,87% pure by GC) which was used in the next stage without furtherpurification.

4-methylthio-2-phenoxypyrimidine (2.00 g, 7.96 mmol) in glacial aceticacid (12 ml) was treated with a solution of potassium permanganate (1.60g, 10.11 mmol) in water (20 ml) as described above for4-chloro-2-methylthiopyrimidine. Work up as before gave a pale yellowoil, which on trituration with ether and n-hexane afforded a paleyellow, slightly sticky powder (1.00 g). Recrystallisation from carbontetrachloride/chloroform (trace)/n-hexane gave4-methanesulphonyl-2-phenoxypyrimidine as a white powder (0.70 g, 35%yield) mp 86°-7° C., ¹ H NMR delta 3.19(3H, s)ppm; IR maxima (nujol)1135, 1305 cm⁻¹.

To a solution of 4-methanesulphonyl-2-phenoxypyrimidine (300 mg, 1.20mmol) in dry DMF (4 ml) was added anhydrous potassium carbonate (116 mg,1.20 mmol). A solution of (E)-methyl2-(2-hydroxyphenyl)-3-methoxypropenoate (0.250 g, 1.20 mmol, prepared asdescribed in Example 3 of EP-A-0242081) in DMF was added and thereaction mixture was stirred at room temperature overnight. It waspoured into water and extracted with ether. The ether extracts werewashed with brine, dried and concentrated to give a yellow oil (0.48 g).Chromatography (eluent ether:n-hexane, 3:1) gave a white solid (0.34 g).Recrystallisation from carbon tetrachloride/dichloromethane(trace)/n-hexane gave the title compound as a white powder (0.31 g, 69%yield); mp 114°-115° C., ¹ H NMR (270 MHz) delta: 3.60 (3H,s); 3.74(3H,s); 6.43 (1H,d); 7.11-7.42 (9H,m); 7.46 (1H,s); 8.28 (1H,d) ppm.

Mass spectrum m/e 378 (M+).

EXAMPLE 3

This example illustrates the preparation of (E)-methyl2-[2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenyl]-3-methoxypropenoate(compound No. 9 of Table I).

To a solution of 4,6-dichloropyrimidine (0.76 g, 5.10 mmol) in dry DMF(4 ml) at 0° C. was added anhydrous potassium carbonate (0.70 g, 5.10mmol). A solution of (E)-methyl 2-(2-hydroxyphenyl)-3-methoxypropenoate(0.53 g, 2.55 mmol, prepared as described in Example 3 of EP-A-0242081)in dry DMF (2 ml) was then added dropwise with stirring. After theaddition was complete, the reaction mixture was allowed to warm to roomtemperature and stirring continued over the weekend. The reactionmixture was then diluted with water (15 ml) and extracted with ether(3×20 ml). The combined ether extracts were washed with brine and dried.Evaporation afforded a brown liquid (1.10 g) which was chromatographed(eluent ether:n-hexane, 3:2) to give (E)-methyl2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxypropenoate as a thick,pale yellow oil (0.58, 71% yield) which crystallised on standing.Recrystallisation from ether/dichloromethane (trace)/n-hexane at -78° C.gave the product as a white powder (0.25 g), mp 94°-5° C. In a separatepreparation, 15 g of product was obtained from 4,6-dichloropyrimidine(15.90 g), (E)-methyl 2-(2-hydroxyphenyl)-3-methoxypropenoate (14.80 g)and anhydrous potassium carbonate (19.64 g).

(E)-Methyl 2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxypropenoate(1.50 g, 4.68 mmol) was heated overnight at 95°-100° C. with2-cyanophenol (0.61 g, 5.15 mmol) and potassium carbonate (0.71 g, 5.15mmol) in DMF (35 ml) in the presence of a catalytic amount of copper(I)chloride. The reaction mixture was cooled, diluted with water and thenextracted with ether. The combined ether layers were washed with 2Msodium hydroxide solution and brine and then dried. Evaporation of thesolvent gave a pale yellow oil (1.52 g). Recrystallisation fromether/dichloromethane/n-hexane gave the title compound as a pale yellowpowder (1.20 g, 64% yield), mp 110°-111° C.; ¹ H NMR delta: 3.63(3H,s);3.74(3H,s); 6.42(1H,s); 7.19-7.47(6H,m); 7.50(1H,s); 7.62-7.75(2H,m);8.40(1H,s)ppm. In a subsequent preparation of the title compound,recrystallisation gave a white crystalline solid, mp 118°-119° C.

EXAMPLE 4

This example illustrates the preparation of (E)-methyl2-[2-(6-[2-hydroxyphenoxy]pyrimidin-4-yloxy)phenyl]-3-methoxypropenoate(compound No. 26 of Table I).

A mixture of catechol (6.6 g, 0.06 mol) and anhydrous potassiumcarbonate (8.28 g, 0.06 mol) in dry DMF (100 ml) was heated for one hourat 110° C. A catalytic amount of copper(I) chloride (0.2 g) was thenadded followed by a solution of (E)-methyl2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxypropenoate (12.82 g,0.04 mol, prepared as described in Example 3) in dry DMF (50 ml). Thereaction mixture was heated at 110° C. for two hours, left to standovernight, and then poured into water. The resulting mixture wasextracted with ether ("extract A"). The remaining aqueous layer wasacidified with concentrated hydrochloric acid and then extracted againwith ether, these second extracts then being washed with water (×3),dried and evaporated to give a brown gum (6.78 g, "extract B"). "ExtractA" was washed with dilute sodium hydroxide solution, and the resultingaqueous phase was acidified with concentrated hydrochloric acid andextracted with ethyl acetate, this ethyl acetate extract then beingwashed with water, dried and evaporated to give a brown gum (6.68 g,"extract C"). Extracts "B" and "C" were combined and thenchromatographed (eluent ether) to afford the title compound (7.8 g,49.5% yield) as a yellow solid which was identical to a sample preparedearlier on a smaller scale, mp 159°-161° C., IR max. 3100, 1712, 1642cm⁻¹ ; ¹ H NMR delta: 3.61 (3H, s); 3.75 (3H, s); 6.30 (1H, s); 6.52(1H, s); 6.91-6.97 (1H, m); 7.05-7.21 (4H, m); 7.26-7.48 (3H, m); 7.45(1H, s); 8.44 (1H, s)ppm.

EXAMPLE 5

This example illustrates the preparation of (E)-methyl2-[2-(6-(2-methoxyphenoxy)pyrimidin-4-yloxy)phenyl]-3-methoxypropenoate(compound No. 29 of Table I).

To a stirred solution of (E)-methyl2-[2-(6-[2-hydroxyphenoxy]pyrimidin-4-yloxy)phenyl]-3-methoxypropenoate(0.50 g, 1.27 mmol, prepared as described in Example 4) in dry DMF (15ml) at 0° C. was added anhydrous potassium carbonate (0.17 g, 1.27 mol)and methyl iodide (0.22 g, 1.52 mmol). The reaction mixture was allowedto warm to room temperature, stirred for two hours and then left tostand over the weekend. The mixture was diluted with water (20 ml) andthen extracted with ether (3×25 ml). The combined ether extracts werewashed with dilute sodium hydroxide solution (2×20 ml) and brine (20 ml)and then dried. Evaporation gave a pale pink foam (0.36 g) which waschromatographed (eluent ether-hexane, 7:1) to afford the title compoundas a white foam (0.21 g, 40% yield); ¹ H NMR delta: 3.60 (3H, s); 3.76(3H, s); 3.78 (3H, s); 6.25 (1H, s); 6.95-7.52 (8H, m); 7.49 (1H, s);8.42 (1H, s)ppm.

In an alternative preparation, (E)-methyl2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxypropenoate (1.00 g,3.12 mmol, prepared as described in Example 3) was treated with sodiummethanethiolate (1.09 g, 15.60 mmol) at room temperature in chloroform(15 ml) and water (10 ml) in the presence of a catalytic amount oftetrabutylammonium bromide. After stirring overnight, the chloroformlayer was separated and the remaining aqueous layer was furtherextracted with chloroform. The combined chloroform layers were washedwith water, dried and evaporated to give an orange oil (1.56 g).Chromatography (eluent ether-hexane, 2:1) gave (E)-methyl2-[2-(6-methylthiopyrimidin-4-yloxy)phenyl]-3-methoxypropenoate as apale yellow oil (0.92 g, 89% yield); ¹ H NMR delta: 2.52 (3H, s); 3.59(3H, s); 3.73 (3H, s); 6.55 (1H, s); 7.17 (1H, d); 7.20-7.55 (3H, m);7.45 (1H, s); 8.57 (1H, s)ppm.

The product (0.20 g, 0.6 mmol) was stirred overnight withmeta-chloroperbenzoic acid (0.38 g of 55% pure material) in chloroform(25 ml) at room temperature. Work-up gave the corresponding sulphone(0.26 g, 94% pure by gc) as a thick, colourless oil which was useddirectly in the next stage without further purification, ¹ H NMR delta:3.25 (SO₂ CH₃), 7.45 (olefinic proton)ppm.

To a stirred solution of the sulphone (0.24 g) in dry DMF (6 ml) wasadded anhydrous potassium carbonate (0.091 g) and a solution of2-methoxyphenol (0.082 g) in dry DMF (2 ml). The reaction mixture wasstirred for four hours and then overnight at room temperature, dilutedwith water (15 ml) and then extracted with ether (3×20 ml). The combinedether extracts were washed with dilute sodium hydroxide solution (2×15ml) and brine (15 ml) and then dried. Evaporation gave a thick, paleyellow oil (0.25 g). Chromatography (eluent ether-hexane, 7:1) affordedthe title compound as a sticky, white foam (0.17 g, 63% yield), ¹ H NMRas before.

EXAMPLE 6

This example illustrates the preparation of (E)-methyl2-[2-(6-(2-thiocarboxamidophenoxy)pyrimidin-4-yloxy)phenyl]-3-methoxypropenoate(Compound No. 59 of Table I).

Excess hydrogen sulphide gas was bubbled through a stirred solution of(E)-methyl2-[2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenyl-3-methoxypropenoate(2.09 g, 15.19 mmol, prepared as described in Example 3) andtriethylamine (0.52 g) in dry pyridine (45 ml) at 50° C. After 41/2hours at 50° C. and one week at room temperature, excess hydrogensulphide was removed by passing air through the reaction mixture. Theresulting brown solution was evaporated and azeotroped with toluene(2×50 ml) to give a brown oil, which was triturated with water (3×40ml). The residue was chromatographed (eluent acetone-hexane, 2:3) toafford a pale yellow oil (0.79 g). Trituration with hexane gave thetitle compound as a pale orange powder (0.68 g, 30% yield) mp 125°-128°C. A sample prepared subsequently had mp 131°-3° C., ¹ H NMR delta: 3.63(3H, s); 3.78 (3H, s); 6.27 (1H, s); 7.18 (1H, d); 7.10-7.60 (6H, m);7.49 (1H, s); 7.71 (1H, s); 7.91 (1H, s); 8.05 (1H, dd); 8.39 (1H,s)ppm.

EXAMPLE 7

This example illustrates the preparation of: ##STR22##

To a stirred mixture of (E)-methyl2-(2-hydroxyphenyl)-3-methoxypropenoate (2.43 g, prepared as describedin Example 3 of EP-A-0242081) and anhydrous potassium carbonate (1.61 g)in dry DMF (25 ml) at 0° C., was added dropwise a solution of2,4,6-trichloropyrimidine in dry DMF (5 ml). The reaction mixture wasstirred for 30 minutes at 0° C. and over the weekend at room temperatureand then poured into water and extracted with ether (×3). The combinedether extracts were washed with dilute sodium hydroxide solution andwater (×3) and then dried. Evaporation afforded an orange gum (2.62 g)which was chromatographed (eluent ether-hexane mixtures) to give(E)-methyl2-[2-(2,4-dichloropyrimidin-6-yloxy)phenyl]-3-methoxypropenoate (0.65 g)as an off-white solid, mp 88°-90° C., and a mixture (1.07 g, approx 1:1)containing: ##STR23##

To a stirred solution of part of this mixture (0.97 g) in THF (25 ml)were added 5% Pd/C catalyst (0.11 g) and then, dropwise over 5 minutes,sodium hypophosphite (0.405 g) in water (5 ml). After stirring at roomtemperature for two hours, the temperature was raised to 60° C. andadditional portions of sodium hypophosphite (0.41 g) in water (5 ml)(after a further 30 minutes) and potassium carbonate (0.76 g) andpalladium catalyst (0.11 g) (after a further one hour) were added. Whenthe starting materials had been consumed (GC and TLC analysis) thereaction mixture was filtered through celite, washing the plug withether and water. The layers of the filtrate were separated and theaqueous layer was extracted with more ether. The combined ether layerswere washed with water (×2), dried and evaporated to give a white foam(0.78 g). Chromatography (eluent ether) gave compound No. 123 of TableI, eluted first, as a white solid (0.34 g); mp 130°-131° C.; IR max.1705, 1693, 1636 cm⁻¹ ; ¹ H NMR delta: 3.59 (6H, s); 3.75 (6H, s); 6.16(1H, s); 7.14-7.18 (2H, m); 7.24-7.41 (6H, m); 7.45 (2H, s); 8.39 (1H,s) ppm; and compound No. 123 of Table II as a white foam (0.23 g); mp60°-70° C.; IR max. 1706, 1632 cm⁻¹ ; ¹ H NMR delta: 3.56 (3H, s) 3.58(3H, s); 3.70 (3H, s); 3.74 (3H, s); 6.34-6.37 (1H, d); 7.15-7.35 (8H,m); 7.44 (1H, s); 7.47 (1H, s); 8.21-8.24 (1H, s)ppm.

EXAMPLE 8

This example illustrates the preparation of (E)-methyl2-[2-(4-fluoropyrimidin-6-yloxy)phenyl]-3-methoxypropenoate, anintermediate for the synthesis of compounds of the invention.

A mixture of 4,6-dichloropyrimidine (6.50 g), sulphur tetrafluoride(20.8 g) and Arcton 113 (35 ml) was heated at 50° C. with stirring in a100 ml Monel reactor for 3.3 hours. The temperature was increased to100° C. over 25 minutes and maintained at 100° C. for a further 3 hours.The temperature was increased to 151° C. over 20 minutes and maintainedat 151° C. for 3 hours. The vessel was then allowed to cool to roomtemperature. The reaction mixture was poured into saturated sodiumhydrogen carbonate solution and extracted with dichloromethane. A stickysolid was observed at the interface and was removed by filtration. Thelayers were then separated. The organic layer was washed with water, andthen distilled at atmospheric pressure to remove the dichloromethane.4,6-Difluoropyrimidine was isolated by distillation in vacuo (50° C./100mmHg) as a light yellow oil (400 mg; 7.3% yield); ¹ H NMR delta: 6.61(1H, s); and 8.69 (1H, s)ppm.

To a solution of (E)-methyl 2-(2-hydroxyphenyl)-3-methoxypropenoate (359mg, 1.724 mmol, prepared as described in Example 3 of EP-A-0242081) indry DMF (3 ml) at room temperature was added dry potassium carbonate(476 mg, 3.45 mmol) in one portion. The reaction mixture was stirred atroom temperature for 20 minutes, then a solution of4,6-difluoropyrimidine (200 mg) in dry DMF (2 ml) was added, viasyringe, over approximately 1 minute. The reaction mixture was thenstirred for a further 20 hours at room temperature, poured into water(20 ml) and extracted with ethyl acetate (4×30 ml). The combinedextracts were washed successively with water (2×100 ml) and withsaturated brine (1×100 ml), then dried and concentrated to give thetitle compound as a sticky yellow oil (464 mg; 88% yield); ¹ H NMRdelta: 3.59 (3H, s); 3.73 (3H, s); 6.32 (1H, s); 7.16-7.43 (4H, m); 7.45(1H, s); 8.51 (1H, d)ppm.

The following are examples of compositions suitable for agricultural andhorticultural purposes which can be formulated from the compounds of theinvention. Such compositions form another aspect of the invention.Percentages are by weight.

EXAMPLE 9

An emulsifiable concentrate is made up by mixing and stirring theingredients until all are dissolved.

    ______________________________________                                        Compound No. 9 of Table I 10%                                                 Benzyl alcohol            30%                                                 Calcium dodecylbenzenesulphonate                                                                        5%                                                  Nonylphenolethoxylate (13 mole                                                                          10%                                                 ethylene oxide)                                                               Alkyl benzenes            45%                                                 ______________________________________                                    

EXAMPLE 10

The active ingredient is dissolved in methylene dichloride and theresultant liquid sprayed on to the granules of attapulgite clay. Thesolvent is then allowed to evaporate to produce a granular composition.

    ______________________________________                                        Compound No. 9 of Table I                                                                              5%                                                   Attapulgite granules     95%                                                  ______________________________________                                    

EXAMPLE 11

A composition suitable for use as a seed dressing is prepared bygrinding and mixing the three ingredients.

    ______________________________________                                        Compound No. 9 of Table I                                                                              50%                                                  Mineral oil              2%                                                   China clay               48%                                                  ______________________________________                                    

EXAMPLE 12

A dustable powder is prepared by grinding and mixing the activeingredient with talc.

    ______________________________________                                        Compound No. 9 of Table I                                                                              5%                                                   Talc                     95%                                                  ______________________________________                                    

EXAMPLE 13

A suspension concentrate is prepared by ball milling the ingredients toform an aqueous suspension of the ground mixture with water.

    ______________________________________                                        Compound No. 9 of Table I                                                                              40%                                                  Sodium lignosulphonate   10%                                                  Bentonite clay           1%                                                   Water                    49%                                                  ______________________________________                                    

This formulation can be used as a spray by diluting into water orapplied directly to seed.

EXAMPLE 14

A wettable powder formulation is made by mixing together and grindingthe ingredients until all are thoroughly mixed.

    ______________________________________                                        Compound No. 9 of Table I                                                                              25%                                                  Sodium lauryl sulphate   2%                                                   Sodium lignosulphonate   5%                                                   Silica                   25%                                                  China clay               43%                                                  ______________________________________                                    

EXAMPLE 15

The compounds were tested against a variety of foliar fungal diseases ofplants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (No 1 or 2) in 4 cmdiameter minipots. The test compounds were formulated either by beadmilling with aqueous Dispersol T or as a solution in acetone oracetone/ethanol which was diluted to the required concentrationimmediately before use. For the foliage diseases, the formulations (100ppm active ingredient) were sprayed onto the foliage and applied to theroots of the plants in the soil. The sprays were applied to maximumretention and the root drenches to a final concentration equivalent toapproximately 40 ppm a.i. in dry soil. Tween 20, to give a finalconcentration of 0.05%, was added when the sprays were applied tocereals.

For most of the tests the compound was applied to the soil (roots) andto the foliage (by spraying) one or two days before the plant wasinoculated with the disease. An exception was the test on Erysiphegraminis in which the plants were inoculated 24 hours before treatment.Foliar pathogens were applied by spray as spore suspensions onto theleaves of test plants. After inoculation, the plants were put into anappropriate environment to allow infection to proceed and then incubateduntil the disease was ready for assessment. The period betweeninoculation and assessment varied from four to fourteen days accordingto the disease and environment.

The disease control was recorded by the following grading:

4=no disease

3=trace -5% of disease on untreated plants

2=6-25% of disease on untreated plants

1=26-59% of disease on untreated plants

0=60-100% of disease on untreated plants

The results are shown in Table V.

    TABLE V        PUCCINIA ERYSIPHE VENTURIA PYRICULARIA CERCOSPORA PLASMOPARA PHYTOPHTH     ORA COMPOUND TABLE RECONDITA GRAMINIS INAEQUALIS ORYZAE ARACHIDICOLA     VITICOLA INFESTANS NO NO (WHEAT) (BARLEY) (APPLE) (RICE) (PEANUT) (VINE)     (TOMATO)       1 I 4 4 4 3 4 4 3 2 I 4 4 4 3 4 4 4 3 I 4 4 4 4 4 4 4 5 I 4 4 4 4b 4 4     4 8 I 4 4 4 3 4 4 4 9 I 4c 4 4 4 4 4 4 10 I 4 4 4 3 4 4 4 11 I 4 4 4 3 4     4 4 13 I 4a 4 4 4 4 4 4 14 I 4 4 4 4 4 4 4 15 I 4 4 4 4 4 4 4 16 I 4 4 4     3 0 4 4 26 I 4 3 4 0 2 4 4 29 I 4 4 4 3 4a 4 4 30 I 4 4 4 4 4 4 4 31 I 4     4 4 3 4 4 4 32 I 4 4 4 4 4 4 4 34 I 3 2 4 2 4 4 0 35 I 3 4 4 0 4 4 2 40     I 4 4 4 3 4 4 4 43 I 4 4 4 3 4 4 4 44 I 4 4 4 2 4 4 4 46 I 4 4 4 1 2 4 4     49 I 4 4 4 4 4 4 4 51 I 4 4 4 0 4 4 4 59 I 4a 4a 4a 2a 4a 4a 4a 62 I 4 4     4 3 4 4 4 63 I 4 4 4 4 4 4 4 1 II 4 4 4 2b 4 4 3 1 III 3b 4b 4b 3b 4b 4b     4b 9 III 4a 3a -- 1a 4a 4a 3a     a 10 ppm foliar spray only     b 25 ppm foliar spray only     c 5 ppm foliar spray only     -- No result

We claim:
 1. A compound having the formula (I): ##STR24## in which anytwo of K, L and M are nitrogen and the other is CE; X is hydrogen,halogen, C₁₋₄ alkyl, C₃₋₆ cycloalkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₂₋₄alkynyloxy, phenyl, benzyloxy, cyano, isocyano, thiocyanato,isothiocyanato, nitro, NR¹ R², NR¹ OR², N₃, NHCOR¹, NR¹ CO₂ R², NHCONR¹R², N═CHNR¹ R², NHSO₂ R¹, OR¹, OCOR¹, OSO₂ R¹, SR¹, SOR¹, SO₂ R¹, SO₂OR¹, SO₂ NR¹ R², COR¹, CR¹ ═NOR², CHR¹ CO₂ R², CO₂ R¹, CONR¹ R² or CSNR¹R² ; Y is thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, dithiazolyl ordioxazolyl, any of which is unsubstituted or substituted with an oxo orthioxo atom, or Y is thiazinyl or oxazinyl, either of which isunsubstituted or substituted with one or two oxo or thioxo atoms; A, B,D, E, G, U, and V are independently hydrogen, halogen, C₁₋₄ alkyl, C₁₋₄alkoxy, cyano, nitro or trifluoromethyl; and R¹ and R² are independentlyhydrogen, C₁₋₄ alkyl, C₂₋₄ alkenyl or phenyl; the aliphatic moieties ofany of the foregoing being optionally substituted with one or more ofhalogen, cyano, OR¹, SR¹, NR¹ R², SiR₃ ¹, or OCOR¹ and the phenylmoieties of any of the foregoing being optionally substituted with oneor more of halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, nitro or cyano.
 2. Acompound according to claim 1 in which any two of K, L and M arenitrogen and the other is CH; A, B, D, G, U and V are all hydrogen; X ishydrogen, halogen, C₁₋₄ alkyl, C₁₋₄ alkyl substituted with halogen,hydroxy, cyano, C₁₋₄ alkoxy or C₁₋₄ alkanoyloxy, C₂₋₄ alkenyl, C₂₋₄alkynyl, C₂₋₄ alkenyloxy, C₂₋₄ alkynyloxy, phenyl, benzyl, cyano,isocyano, thiocyanato, isothiocyanato, nitro, amino, mono- ordi(C₁₋₄)alkylamino, formylamino, C₁₋₄ alkanoylamino, benzoylamino,ureido, phenylureido, C₁₋₄ alkylsulphonylamino, phenylsulphonylamino,hydroxy, C₁₋₄ alkoxy, phenoxy, C₁₋₄ alkanoyloxy, C₁₋₄ alkylsulphonyloxy,phenylsulphonyloxy, C₁₋₄ alkylthio, C₁₋₄ alkylsulphinyl, C₁₋₄alkylsulphonyl, formyl, C₁₋₄ alkanoyl, benzoyl, hydroxyimino(C₁₋₄)alkyl,C₁₋₄ alkoxyimino(C₁₋₄) alkyl, carbamoyl, C₁₋₄ alkylcarbamoyl,thiocarbamoyl or C₁₋₄ alkylthiocarbamoyl, the phenyl ring of any of theforegoing being optionally substituted with halogen, C₁₋₄ alkyl, C₁₋₄alkoxy, nitro or cyano.
 3. A compound according to claim 2 in which Y isattached to the 2-position of the phenyl ring.
 4. A compound accordingto claim 1 in which any two of K, L and M are nitrogen and the other isCH; A, B, D, G, U, V and X are all hydrogen; and Y is attached to the2-position of the phenyl ring.
 5. A fungicidal composition comprising afungicidally effective amount of a compound according to claim 1 and afungicidally acceptable carrier or diluent therefor.
 6. A method ofcombating fungi which comprises applying to plants, to the seeds ofplants or to the locus of the plants or seeds, a fungicidally effectiveamount of the compound according to claim 1.